Process of preparing aralkyl carbonates



Patented Aug. 11, 1953 raoosss 0F PREPARING ARALKYL CARBONATES CharlesAdam Heiberger, Nitro, W. Va., assignor to Ohio-Apex, Inc., Nitro, W.

of West Virginia Va., a corporation No Drawing. Application January 13,1951,

Serial No. 205,967

The present invention relates to a method of preparing organiccarbonates from organic chlorides, which possess a reactive :=c 1-omo1roup such as, for instance, benzyl chloride. More specifically thisinvention relates to the preparation of carbonates from certain of saidorganic chlorides.

In general, organic carbonate esters have been previously prepared inlimited amounts or on a laboratory scale by various methods, includingthe well known methods which comprise either the reaction of alcoholswith phosgene (or with esters of chloroformic acid) or the reaction ofalkyl iodides with silver carbonate. Such methods require relativelyexpensive reactants or special processing techniques or both. Yield isnot always satisfactory, and organic carbonate esters made by suchprocesses are usually not available except in special applications whereexpense is warranted.

The principal object of the present invention is the provision ofmethods by which carbonates, and particularly certain aralkyl and thenylcarbonates, may be prepared in such quantities and at such costs as willinsure the availability of these carbonates as commercially usefulsubstances. Other and more detailed objects will be apparent from thefollowing description of the invention.

The reaction with which this invention is concerned is essentially Aswritten the reaction is not effective to achieve any noticeable yield ofcarbonate. However, I have found that if the reaction is catalyzed bythe addition to the reaction mixture of certain titative reactiverelation to the amount of the reactants. The reaction will proceed aslong as very small amounts of this catalytic compound are present. Itis, of course, desirable to use as little as possible of the catalyticcompound in They are not exhausted during the reaction. The amount ofthe amine which, if present, will promote the reaction has no quan- 10Claims. (Cl. 260332.5)

2 order to minimize cost. Generally, an amount of the catalystcorresponding to about .01 to .1 mol per mol of the organic chloridereactant will produce good yields. Greater amounts are not harmful,except as bull: affects handling of the reaction mixture and may,therefore, somewhat reduce the-yields. 1

The carbonate component of the reaction is either sodium carbonate orsodium bicarbonate, the latter being the-equivalent of the first exceptthat the formation of ether by-products may be somewhat higher when thebicarbonate is used. Both are herein comprehended by the term carbonateof sodium. Corresponding potassium salts are ineffective to producecomparable yields, a drop of 80 to 90 per cent in effective yield beingobserved when attempt is made to substitute the potassium carbonates.Similar ineffective results are obtained with carbonates of ammonium,lithium, zinc, barium, magnesium and calcium. Likewise other organichalides possessingthe I group, the essential carbonate of sodium and thecatalyst. A molar excess of the carbonate component promotes theefiiciency of the reaction. The efiect produced by the excess is one ofefiiciency resulting only in better yield. Economically a molar excessof carbonate is desirable but amounts above about 200 per cent excessusually cease'to be economic, from the standpoint of production in bulk,because yield does not further increase to justify reactant cost. Inaddition, the

mixing or handling difficulties created by an tion medium or menstruum.

overload. of the carbonate may actually decrease yield below the optimumwhich could otherwise'be obtained.

The reaction mixture should be non-aqueous in the sense that water isnot present as a reac- Unsatisfactory yields are obtained when overabout 2 per cent of free water by weight of the total reaction mass ispresent. Whenever possible, conditions should be adjusted to excludemoisture and preferably the free moisture content of the reactionmixture should be; less than 1 per cent by weight for best results.Water present in the mixture and combined physically orchemically to theextent that it is 'not available as moisture does not seriously aifectthe reaction.

The reaction does not normally proceed with any real effect below about50 centigrade. The efiiciency of the reaction increases as thetemperature rises and usually will be found to be commerciallysatisfactory at betweenSO and 130 centrigrade, the optimum yield beingusually achieved within this range. A limiting factor in reactiontemperature, apart from cost, is one of decomposition or polymerizationof the reaction furnishing the group. Sometimes such components: willeconomically permit of higher reaction temperatures where polymerizationor decomposition is slight. The reaction will not be blocked by suchhigher temperatures but yields, of course, will be reduced, at least tothe extent that the amount of component containing the group isdiminished. Subject to these considerations reaction temperatures ashigh as 150 C. can be used.

The nature of the compound containing the group does not appear toprevent an improved effect caused by the use of the. catalyst. From acommercial standpoint, however, yield may be afiected by polymerization,by the molecular bulk of the radical to which the chloride group isattached, and likewise by strongly polar groups, such as nitro groups,which by number or effect reduce the reaction. efiiciency of the group.Reaction efficiency may also be'affected by the position of othergroups.

The specific chloride compounds which are of greatest usefulness tocarbonate'production in accordance with this invention, from thestandpoint of reaction efiiciency, stability of the group in thereaction. mixture and. absence of strongly polar groups or other groupswhich inhibit or prevent realization of the full potentialities of thereaction, are those selected from the class consisting of benzylchloride, naphthobenzyl chloride, thenyl chloride, methyl substitutednaphthobenzyl chlorides, benzyl, naphthobenzyl and thenyl chloridessubstituted with not more than two halogens of atomic numbers greaterthan 9, and such benzyl and halogen substituted benzyl chlorides as aresubstituted with substituents, which are selected from the classconsisting of alkyl, alkoxy, phenyl and phenoxy groups, the totalcarbons of all such substituents being less than 7;

Examples of specific chlorides of this class are: benzyl chloride;methyl benzyl chloride; ethyl benzyl chloride; isopropyl benzylchloride; sec ondary butyl benzyl chloride; amyl benzyl chloride; hexylbenzyl chloride; dimethyl benzyl chloride; 2,4 dimethyl benzyl chloride;diethyl benzyl chloride; diisopropyl benzyl chloride; trimethyl benzylchloride; 2,4,6 trimethyl benzyl chloride; triethyl benzyl chloride;pclymethyl benzyl chloride; Z-methyl, E-isopropyl benzyl chloride;methyl, amyl benzyl chloride; ethyl, sec. butyl benzyl chloride;ortho-chlor benzyl chloride; para-chlor benzyl chloride; 2,4 dichlorbenzyl chloride; 3,4 dichlor benzyl chloride; brom benzyl chloride;chlor dimethyl benzyl chloride; dichlor dimethyl benzyl chloride;5-brorn 2,4-dirnethyl benzyl chloride; iododimethyl benzylchloridegbrom, sec. butyl benzyl chloride; orth o-chlo r para-amylbenzyl chloride; iodo ethyl benzyl chloride; dibrom benzyl chloride;ethoxy benzyl chloride; diethoxy benzyl chloride; butoxy benzyl...chloride; Z-ethoxy, 4-but'oxy benzyl chloride; phenylbenzyl chloride;phenoxy benzyl chloride; I

3-brom0 4 amyloxy benzyl chloride; 2-iodo l-phenyl benzyl Y chloride;para-promo, phenyl benzyl, chloride;

2-chlor 4-ethoXy benzyl chloride;

are each satisfied by attachment to a carbon atom of an organic group,no more than two of such valences being satisfied by a single carbonatom. In general the tertiary amines and quaternary ammonium compoundswhich have three nitrogen valences satisfied as above described areeffective as catalysts to some degree. Morpholine does not have acatalytic efiect but when substituted to satisfy the valence requirements above set forth, the so substituted morpholine has catalyticeffect as do also the morpholinium halides wherein nitrogen valences aresatisfied as above mentioned. Pyridine, the substituted pyridines andtriethanol amine have, for example, nitrogens the. valences of which areeach satisfied by attachment to carbon atoms of an organic group, withno more than two of said valences being satisfied by a single carbonatom, and these 00.1. pounds are catalytic in the reaction hereindescribed. Urea, in which the nitrogen valences are not so satisfied, isnot catalytic in action, but substituted ureas in which at least one ofthe nitrogens has its valences so satisfied are catalytic. From thestandpoint of efficiency these nitrogen compounds are not equal incatalytic effect, some being more active than others and many being,from a commercial standpoint, of a such limited activity as to precludetheir use in large scale processes,

Those nitrogen compounds of the type above described best suited to thepurposes of my invention from the standpoint of efficiency are selectedfrom the class consisting of the compounds set forth in Table I.

Table. I

1. Pyridine;

2. Methyl pyridines;

3. Triethanol amine;

4. Ureas of general formula atoms;

6. Tertiary amines of general formula R RAN wherein R is as abovedefined; wherein Rb represents a group selected from the classconsisting of unsubstituted alkyl groups of less than 19 carbons, ethyl,propyl and benzyl groups having less than three hydrogens thereofreplaced by groups selected from the class consisting of NR'z and OH,substituted alkyl groups of less than 21 carbons, no more than 6 ofwhich are ring bound carbons, wherein hydrogen is replaced with a groupselected from the class consisting of the substituent groups phenyl,phenoxy, alkenyl, alkenyloxy, alkyl, alkoxy, halogen substituted phenyland halogen substituted phenoxy groups, and any of said substituentgroups wherein a hydrogen thereof is replaced by another of said 6Examples of the catalysts defined by general formula's'et forth in TableI include: tri ethyl amine; tri methyl amine; di methyl, octadecylamine; di ethyl, butyl amine; tri isopropyl amine; tri butyl amine; triamyl amine; tri hexyl amine; di amyl, butyl amine; ethyl, isopropyl,dodecyl amine; di butyl, octyl amine; methyl,

hexyl, nonyl amine; di methyl, (phenyl methyl)v amine; di ethyl, (phenylmethyl) amine; di methyl, (hyroxy phenyl methyl) amine; di ethyl,(diethyl amino ethyl) amine; di ethyl, (amino propyl) amine; di methyl,(hydroxy isopropyl) amine; di ethyl, (hydroxy ethyl) amine; propyl,ethanol amine; di ethyl, isopropanol amine; methyl, propyl, aminopropylamine; di ethyl, dibutyl aminoethyl amine; di propyl, hydroxybenzylamine; methyl, ethyl, dimethylbenzyl amine; di isopropyl, aminobenzylamine;

di methyl, ethyl hydroxy benzyl amine; ethyl, isopropyl, ethoxybenzylamine; diethyl, dichlorbenzyl amine; di propyl, iodobenzyl amine; dimethyl, methoxy bromobenz'yl amine; methyl, dipropanol amine; ethyl,bis(dimethylbenzyl) amine; isopropyl, ethanol, aminopropyl amine;methyl, dibenzyl amine; methyl, diethylaminopropyl, benzyl amine; ethyl,methoxy iodobenzyl, ethanol amine; methyl, ethylbenzyl, aminoethylamine; ethyl, bis(aminoethyl) amine; dimethyl, octylphenoxyethoxyethylamine, methyl, isopropyl, butenyl amine; di ethyl, octadecenyl amine; dipropyl, eicosenyl amine; methyl, ethyl, 2,5-hexadienyl amine; di methyl,phenylbutyl amine; di ethyl, dipropylphenyl hexyl amine; methyl,isopropyl, methoxy butyl amine; di-

- propyl, phenoxydecyl-amine; di methyl, stearyl amine; di butyl,(phenyl methyl) amine; amyl, di(aminopropyl) amine; methyl, hexyl,aminobenzyl amine; methyl, aminobutyl, ethoxymethyl amine; isopropyl,butoxyethyl, hydroxyisopropyl amine; butyl, amyl, nonenyl amine; hexyl,orthochlorbenzyl, ethanol amine; ethyl, octenyl, phenoxybutyl amine;methyl, propenyloxyethyl, octadecyl amine; N-methyl, N-butyl. hydroxybenzyl amine;'ethyl, aminopropyl, butoxymethyl amine; methyl, butyl,ethylphenoxymethyl amine; isopropyl, dibutylaminoethyl, hexadecenylamine; di hexyl, hydroxy ethyl amine; methyl morpholine; ethylmorpholine;

- amyl morpholine; methyl, butoxymethyl morsubstituent groups, thehalogens contained in said halogen substituted groups being of atomicnumber greater than 9 and replacing less than 3 hydrogens of saidgroups; and wherein Ra represents any group selected from the class ofRb groups except unsubstituted alkyl groups having more than 6 carbonatoms and substituted alkyl groups having more than 9 carbon atoms;

'7. Morpholinium halides of general formula /R o04HaN X wherein R and Raare as above defined and X represents a halogen; and

8. Quaternary ammonium compounds corresponding to any of the generalformulas monium hydroxide;

pholinium bromide; ethyl, benzyl morpholinium bromide; isopropyl,octenyl morpholinium chloride; butyl, propoxybutyl morpholinium iodide;hexyl, hydroxyethyl morpholinium chloride; methyl, phenoxypropyl'morpholinium chloride; propyl, aminopropyl morpholinium bromide; amyl,butyl morpholinium chloride; isopropyl, propenyloxymethyl morpholiniumiodide; tetrabutyl urea; 1,1 dibutyl urea; 1,1 di methyl urea; 1,1diethyl urea; tetra ethyl urea; tri propyl urea; alpha picoline; betapicoline; gamma picoline; tetra methyl ammonium fluoride; tri ethyl,octadecyl ammonium iodide; ethyl, di-

propyl, dodecyl ammonium chloride; tetra ethyl ammonium bromide; dimethyl, ethyl, hexadecyl ammonium bromide; tri methyl, hexadecylammonium bromide; di propyl, amyl, dodecyl amtri ethyl, dimethylbenzyl Iammonium chloride; tri ethyl, benzyl ammonium bromid'e; tri ethyl,benzyl ammonium chloride;

di methyhdodecyl, benzyl ammonium chloride; di methyl, octadecyl, benzylammonium chloride; tri methyl, benzyl ammonium hydroxide;

tri methyl, benzyl l ammonium butoxide; di

wherein R, R, Ra, Rb and X are as above defined.

methyl, butyl, butenyl ammonium fluoride; di

methyl, dodecyl, benzyl ammonium fluoride; di

methyl, aminoisopropyl,benzy1 ammonium methoxide; tri ethyl,hydroxyethyl ammonium hydroxide; methyl, dipropyl, octadecenyl ammo--niumv ethoxide; di methyl, octylphenoxyethoxy ethyl, benzyl ammoniumchloride; tri ethyl.am monium hydrochloride; methyl, diisopropylammonium acetate; di butyl, hydroxybenzyl, ammonium hydrobromicle; dipropyl, diethylaminobenzyl, octenyl ammonium iodide; ethyl, butyl,propenyloxymethyl, chlorbenzyl ammonium chloride; dimethyl, ethyl,octadecenyl ammonium bromide; diethyl, bis(aminoisopropyl) ammoniumbromide; di methyl, bis(hydroxyethyl) ammonium iodide; di isopropyl,hydroxypropyl ammonium sulfate.

The efiectof the specific chloride reactant on the efficiency of thereaction and the ,efiect of the use of a specific catalyst .aregenerally illustrated. by, the examples set forth in Tables 11, III, IVand V.

Each example. set forth in said tables represents the result obtainedwhen a reaction mixture composed of carbonate reactant, the namedchloride reactant and the named catalyst was reacted for a number ofhours and the crude reaction product distilled or otherwise treated toobtain the carbonate. The carbonate reactant was carbonate of sodium andin most cases was used in molar excess of' the chloride reactant.

Table II illustrates-the efficiency of a preferred catalyst,triethylamine, when used with various chloride reactants. The productshown in this table is the simple ester derived from the indicatedchloride except in 'the last three examples given where themixed esterwas produced.

Table II Amount of Amount of r catallyst, (Llarbgnatte Tempera- 1110 perro uc ture of Reaction Chlonde Reactant 'mol of formed, Reaction, time,hrs.

chloride percent of C. reactant theoretical .056 35. 9 90 24. .056 71. 3100 24 056 72. 1 110 24 .056 75.8 120 24 .056 68. 8 130 24 .056 '28. 9110 2 .056 53. 7 110 5 .056 69. 8 110 10 056 77. 3 110 15 022 51. 2 11020 036 75. 8 110 20 056 79. 8 110 20 072 82. 1 110 20 .108 79.1 110 20.056 67. 3 100 24 .056 61. 4 100 24 .056 57. 6 100 24 056 36. 100 24.056 54. 3 110 20 056 72. 7 110 20 056 77. 4 110 20 056 78. 5 110 20 05683. 1 110 20 Do .055 77. 7 110 20 Methyl Benzyl 072 86. 4 110 2r) EthylBenzyl .072 82. 6 110 iso-Propyl Benzyl .072 56, 4 100 24 sec-BntylBenzyl 072 34. 7 100 24 Do 051 58. 5 110 15 Amyl Benzyl .07 38. 2 100 24Di-isopropyl Benzyl 072 35. 1 100 24 Diethyl Benzyl .0 2 51.0 100 24 Do072 66. 6 110 20 Do.. .0 2 47. 9 100 24 Methyl, lsopropyl Benzyl 07 39.2 100 24 Polymethyl Benzyl 72 70. 7 100 24 Do 072 74. 7 110 22 2,4,6Trimethyl Benzyl .072 26. 5 100 24 (ortho) Dimethyl Benzyl... .072 76.9100 24 (meta) Dimethyl Benzyl.-. .072 77. 7 100 24 (para) DimethylBenzyl .072 77.5 100 24 (3) Dimethyl Benzyl .072 80.0 100 24 DimethylBenzyl .072 81. 2 100 24 (3) Dimethyl Benzyl .004 16.0 100 (10) DimethylBenzyl .014 58. 7 100 24 Do .029 77.7 100 24 .042 78. 2 100 24 .058 77.7 100 24 .072 76. 3 100 24 108 75. l 100 24 .080 88 90 .080 81 100 20.080 74 110 20 080 120 20 072 40. 7 100 24 .072 45. 9 100 20 .072 69.0100 20 072 73. 4 100 20 072 80. 2 100 20 .072 77.9 100 20 .072 64. 9 10020 072 82. 4 100 24 072 78. 4 100 24 .072 71. 2 100 24 .072 76. 9 20.072 57.2 5 .072 82. 3 100 10 .072 84. 3 100 15 072 81. 6 100 20 072 78;2 20 Do .072 76. 7 20 (Industrial) Dnnethyl BenzyL. .072 73. 3 100 24 o036 58.0 100 24 me y y .936 .32. 0 I 100 24.

Table II-C'ontmued Amount of Amount of catallyst, Clarbgnage Tgmperfa- Ru mo per ro uc ure eac on Chloride Reactfmt mol'pf formed, Reaction,time, hrs."

: chloride percent of C.

reactant theoretical Naphthobenzyl 064 30. 8 100 24 Do 068 42. 110-12020 Methyl Naphthobenzyl 072 83. 6 100 24 Dlmethyl Naphthobenzyl 078 64100 24 Ethoxy Benzyl 036 63. 5 90 15 Phenoxy Benzyl 072 36. 8 100' 24Thenyl 072 13 100 19 ortho-Ohlor Benzyl 056 52. 7 100 24 D0 -4 056 59. 7110 24 D0 056 56. 0 120 24 Do 072 70. 0 100 24 Do 072 as. 3 110 24 paraOhior Benzyl 072 78. 0 110 20 2,4 Dichlor Benzyl. 072 67. 8 110 22 3,4Dichlor Benzy1 072 35. 3 100 23 D0 .072 68.8 110 20 Chlor (10) DimethylBenzyl 072 59. 0 100 Do 072 75. 8 100 24 Iodo (Industrial) DimethylBenzyl 072 41.0 100 16 Benzy1+3,4 Dichlor Benzyl 072 20 110 20 D0... 07248 110 20" BenzyH-Ethyl Benzyl 072 100 2E0 Table III illustrates theaction of catalysts of 25 general formula RRaRbN and of correspondingquaternary ammonium compounds of the general formulae RRaRbl-RKNX,RRaRbRNOR', RRaRbHNOOCR' 1 dicated chloride.

and RRaRbI-INOSOzOH. The product shown in the table is the simpleesterderived from the in- Table III Amount of Amount of I catalyst, moi3x332? Tempera- R Chloride Reactant Catalyst per mol of armed. ture ofRechloride recent em action, "0.

actant retica] 056 41. 6 90 24 056 40. 9 100 24 056 66. 0 110 23 056 73.6 120 24 056 32.0 90 24 056 47. 1 100 25 056 64. 2 110 24 056 65. 2 12024 032 38. 1 100 24 056. 53. 0 120 24 056 54. 1 '120 24 do... .056 63. 9130 24 Trihexyl amine. 072 40. 3 120 24 N, N Diethyi Benzyiamine .07229.0 100 24 N, N Dibutyl Benzyl Amine .072 9. 9 100 24 Triethylbenzyiammonium chloride. 072 65. 8 120 24 Triethyi benzyl ammonium bro- 05556. 3 110 23 m e. Aug], (ilimethyL-benzyl ammonium 072 62. 9 120 24 c ore. Algyl, ddimethyhbenzyl ammonium 036 32. 5 110 15 non e. (10) DimethylBenzyl. 'Irimethyl amine 072 20. 9 100 24 Dimethyl Benzyi Tri-n-propyiamine. 072 60. 3 100 24 Do do 072 49. 9 110 24 Do (10---- 072 45. 9 12024 Do Tri-n-butyl amine 072 10. 6 90 24 D0- (10.--- .072 35. 4 100 24 Do.072 52. 6 110 24 Do -.do 072 54. 2 120 24 Do Triamyl amine 072 24. 0100 24 Do- 072 36. 3 110 24 Do 072 58. 1 120 24 Do 072 35. 1 100 24(ortho) Dimethyl BenzyL. .072 53.4 110 24 (10) Dimethyl Benzyl. .d0 07243. 9 120 24 Do Diethyl, butyl amine- 072 72. 3 100 24 Butyi, diamyiamine 072 24. 5 100 24 Dimethy], oetadecyl amine. 072 46. 5 100 20 07245. 4 110 20 rln .072 86 120 20 N,N Dimethyi, benzyl amine; .072 49. 7100 2O fin .072 73. 9 110 20 do 072 73. 7 120 20 N,N Diethyl benzylamine. 072 26. 0 100 24 N,N Dibuty], benzyi amine 072 15. 1 100 24 N,NDlmethyl; hydroxy 072 20 amino.

do 072 53. 5 20 072 49. 7 20 Dimritlhyl, octylphenoxyethoxyethyl 072 48.3 100 20 am e. Dlethylaminomethyl, diet hyi 042 20.9 100 23 amine.

fin 126 14. 2 100 24 (in 072 20. 4 110 20 (in 072 28. 4 120 20Aminopropyl, diethyl amine.. 072 55 100 20 Amount of Amount of ,7 V .cay t 55E333? mpera- Reaction. Chloride Reactant Catalyst per mol of fture of Reh chloride re- Ormed' action C tune 80mm cent of theoretical(ortho) Dimethyl BenzyL. Hydroxyisopropyl, dimethyl amine .036 46. 11015 o Hydroxyethyl, diethylamme.. .036 40.5 100 1'5 (Solvesso) DimethylBen- Methyl, diethanol amine .072 42.0 110 15 Z (10) Dimethyl BenzylTriethyl, dimeth'ylbenzyl ammo- .072 65.4 100 24 nium chloride. DoDimethyl, alkyl, benzyl ammonium .072 52.8 100 24 chloride. DoDimethyl,hexadecyhbenzylammo- .072 55 100 nlum bromide. Do Dimethyl,octadecyl benzyl ammo- .072 55.6 100 20 nium chloride. Do Dimethyl,octadecenyl, ethyl am- .072 40' 100 20 monium bromide. Do Trimethyl,hexadecyl, ammonium .072 100 20,

bromide. (Industrial) Dimethyl Trimethyl, benzyl ammonium bu- .018 23:2100 1'5 Benzyl. tpxi e. (3) Dimethy1Benzyl Tndimetgyh benzyl ammomum by-.036 23. 5 15 roxi e. Do o .036 26.5 110 15 (solves Dimethyl Ben-Tetraethyl ammonium bromide .036 31.0 15" y Triethyl ammoniumhydrochloride. .072 59. 5 15 N,iN-dimethyl benzyl amine .072 55.0 15Dimethyl, octylphenoxyethoxyethyl .072 30. 5 120 15 amine. Diethyl,aminopr0pyl, butox'y- .036 43.0 120 15 methyl ammonium chloride.Trimethyl, benzyl ammonium hy- .036 10.0 110 15 H ld- AmylBenzylTrihexyl amine .072 14.5 120 15 Do Dimethyl, butoxymethyl, benzyl .07218.5 110 15 ammonium chloride.

Diisopropyl Benzyl Dimethyl, hydroxyethyl, ortho- .036 6.5 I10 15 Ichlorbenzyl ammonium chloride. Do Alkgladimethyhbenzyl ammonium .036 28110 15 Phenyl'Benzyl Triamylamine .072 24.5 110 15 Do Trietiyl, benzylammomum bro- .036 26.0 110 15 mi e.

D Alkyl,dimethyl,'benzylammonium .036 34.0 110 15 fluoride.

Do Dimethyl, butoxymethyl, be'nzyl- .036 22.0 110 15 ammonium chloride.

Naphthobenzyl Trime thyhhenzyl ammonium bu- .072 25.5 110 15 toxi e.Methyl Naphthobenzyl Dimethyl, octylphenoxyethoxyeth- .072 17.0 120 15 yamine. Ethoxy Benzyl Tr imet l iyl, 56 3 1 ammon um hy- 036 8.5 100 15roxi e. Do Diethyl, butoi y'methyl, aminopro- .072 28.5 100 15 pammonium chloride. 7 D Alkgladimethyl,benzylammonium .036 6.0 110 15 10l e. Do N,N-dimethyl, benzyl ammonium .072 52.5 110 15 acetate. PhenoxylBenzyl Dimethyl, octylphenoxyethoxyeth- .073 t 18.0 110 15 Y amine. DDiethyl, hydroxyethyl, orthochlor .072 23.0 110 15 benzyl ammoniumchloride.

Theny] Dimethyl, octylphenoxyethoxyeth- .036 28.5 100 15 y amine.

Do Diethyl, aminopropyl, I liutoxy- .036 v 5.0 100 15 methyl ammoniumchloride. 7 I 7 ortho Chlor Benzyl Dlmethyl, butoxymethyl, benzyl .03637.0 110 ammonium chloride.

D Dimethyl, octadecenyl, ethyl am- .036 32.5 110 15 monium bromide. V v7 Do Methyl, diethanol ammonium sul- .036 24.5 110 15 fate. I

para-Chlor Benzyl Aminopropyl, diethylamine .072 52.0 120 15 2,4 DichlorBenzyl DiQethylbutyl) ethanol amine. .072 1; 5 15 Do -1100-.- .072 1 1.0 15 Bromo Dimethyl BenzyL. Trihexylamme .072 24.5 120 15 D Dietliyl,aminopropyl, butoxy- .072 32.0 110 15 methyl ammonium chloride.

Iodo Dimethyl Benzyl Dimethyl, oetylphenoxyethoxyethyli 072 36.0 V 12015 amine. Chlor Naphthobenzyl Tributyl amine .072 1 3 0.5 110 15 DDimethyl, octadecenyl amine. .072 v 30.0 110 15 D Dietliyl, aminopropyl,b utoxy- .036 23.0 7 110 15 methyl ammonium chloride. V 7 7 DN,N-dimethyl, benzyl ammonium .072 34.5 110 15 I acetate.

Dimethyl, octadecyl amine 072 24; 0 100 15 Chlor Thenyl Table IVillustrates the action of catalysts which have a ring bound nitrogensuch as pyridine, methyl pyridines', the substituted morpho 75"rivedfrom the indicated chloride.

lines and the morpholinium halides. The prodnot shown in the table isthe simple ester de- Table IV Amount. of Amount of catalyst,1mfol(iarbmaite Temperfa- Reaction Oatal st or mo r0 uc ureo ChlorideReactant y chloride percent of Reaction, time reactant theoretical 0.

Benz Pyridine .072 26.0 110. 15 Meth Benz Ig-etgyl morpholine" 138 h I BL in ffiiifuffii nnn .012 21.1 90 20 D0- 072 44. 9 100 20 Do 072 22. 1110 20 Do do 072 17.5 120 20 (Ortho) Dimethyl BenzyL N-Metl ylmorpholine .072 17.0 100-120 4. 5 (Solvesso) Dimethyl Benalpha-picolme.072 19.0 100 zyl. see. But 1 Benz 1 gamma-picoline 072 20.0 120 15Phenyl %enzyl Eghylimnzyl morpholinium .036 6. 5 110 15 mm e. Nahthobenzyl N-ethyl niorpholine 072 31. 0 110 15 Methyl N aphthobenzy1Alpha-plcolme 072 1L 0 120 15 Ethoxy Benzyl Pyr 072 30. 5 100 15 DoMethyl,bntoxy-methyl morphohn- 072 5. 6 100 15 I N t l i i 1 072 41 11015 Pheno Benz l. -e y morp 0 me Thenyfi .3- alphapicoline 065 7. 0 10015 ortho-Chlor Benzyl Pyridine 072 19. 5 110 15 2,4 Dichlor Benzyl dn072 12. 5 110 15 Bromo Dimethyl BenzyL. N -methy1 morpholme 072 8. 5 11015 Ohlor Thenyl Methyl butoxymethyl morpholm- 072 30. 5 100 15 iumchloride.

Table V illustrates the action of other catalysts herein described. Theproduct shown in the table is the simple ester derived from theindicated chloride.

as herein defined. Those compounds in which R, R and Ra areunsubstituted alkyl groups of not more than 3 carbon atoms appear, inmany instances, to be the most active catalysts. Gen- Table V Atmlouzitof] imoount of T ca 21 ys mo or one o empera- Reaction t Catal st permol of Product ture of Chloride Reactan y chloride percent 61 Reactiontune reactant theoretical 0.

Benzyl 1,1 Diethyl urea .072 20. 0 120 15 1,1 Dlbut 1 urea. .036 4 10015 gff i 3 Aim- 036 7 110 15 D -d0 036 26 120 15 Do Triet o eu .832 1% 51 3 8 l Tetra ut urea (10)])1gu.n.e t 1:}.7} Benzy y .072 26. 5 110 Do:-.012 27.8 120 20 D Triethanol amine 072 44 4 20 rin .072 17. 5 20 ""i '1'85? 12-8 it; it Ethyl Benzyl. 1,1 D met y urea.

1 1 Dieth 1 urea.. 072 7. 5 120 15 Sec do. i... 23.8 1B 1. Triethanoamme rggl ftholf i z yi 1,1 Dibutyl urea- 072 6. 5 120 15 Do Triethanolammo. 072 15. 5 15 '832 5'3 i Thenyl 00 15 1 072 24. 5 100 15 l%g i 072l. 5 5 83% 13'? 58 i2 l B I titttfittiftfnffiii--. .072 25. o 100 15 b1the desi ations in parentheses which appear before the chloridereactant, dimethyl benzyl, indicate mag; $33339 giea in the riginalchloro-niethylation to prepare the dimethyl benzyl chloride.

general formula RRaRbN, RRaRbRN X, OC4H8N-R and erally the tertiaryamines having three unsubstituted alkyl groups will be, because ofefficiency, availability and cost, of greatest usefuhiess in large scalecommercial production and, of such amines, triethyl amine is preferred.

As the tabulated examples indicate, however, all of the describedcatalysts are useful to positively promote carbonate formation in theotherwise practically inactive reaction between the chloride andcarbonate of sodium, and thus the choice of the catalyst depends uponavailability, cost and the other economics of the particular operationto which the present invention may be applied.

This application is a continuation-in-part of each of my following namedapplications now abandoned: application Serial No. 18,084, filed andwherein R is a substituent selected from the group consisting of.halogen, lower alkyl, lower alkoxy, phenyL. phenoxy, and combinationsthereof, m is a number from zero to five, the number of carbons in thesubstituent being not reater than six; is selected fromnthe groupconsisting of halogen, methyl, and combinations thereof; Y is a halogenand n is a number from zero to two; in thepresence of a nitrogen bearingorganic compound as a cata1yst,,said organic compoundbeingcharacterizedby thefact that three valences of said nitrogen aresatisfied by. attachment to a carbon atom, no more than two of saidvalences being satisfied by the same carbon atom.

2. The process for the production of organic. carbonates which comprisesheating at tempera-- tures of about 50 to about 150 C. amixturein whichfree water is not substantially in excess oftwo percent by weight, themixture. comprising.

carbonate of sodium and a compound selected from the group consisting ofOHzCl CH CI h), 2

and

(IIHgCI wherein R is a substituent selected from the group consisting ofhalogen, lower alkyl, lower alkoxy, phenyl, phenoxy, and combinationsthereof, m is a number from. zero to five, the number'ofcarbons in thesubstituentsbeing. not greater. than: six; X is selected from the groupconsisting of halogen, methyl, and combinations thereof Y is a halogenand n is a number from zero to-twoy in the-presenceof anitrogen bearingorganic compound as a. catalyst, said organic compound beingcharacterized by the: fact .thatthreevalences ofsaid nitrogen. aresatisfied by attachment to a carbonatom, no more than two of saidvalences.beingsatisfied by. the. same carbona-tom.

3. The process set. forth in claim 2. in which thecarbonat'e of sodiumis. present in the'mixture in molar excess of the chloride reactant.

4. The process set forth in claim 2 in which the nitrogen bearing;organic compound is-atertiary amine characterized by. the'fact' thatthreevalences of: its nitrogen are-satisfied by. attachment to a carbonatom, no more than two of; said.

valances being satisfied by the same carbon atom. 5'. The.- process setforth in claim 2 in which the n bearine... r an co oun is. a

quaternary ammonium compound characterized by the fact that threevalences of it nitrogen are satisfied by attachment to a carbonatom, nomore than two of said valences being satisfied by the same carbon. atom.

6. The process set forth in claim 2 in which the. catalyst comprises:triethyl benzyl ammonium chloride. I

'7. The process. set forth in claim 2 in which the catalyst'comprises a.tripropyl amine.

8. The. processsetforthin claim 2 in which the catalyst comprises N,Ndimethyl benzyl amine.

9; The process set forth in claim 2 in which the catalyst is triethylamine.

10-. The process'setf forth in claim the catalystis N-ethylmorpholine.

CHARLES ADAM HEIBERGER'.

2' in Which References Cited in the file of this patent Gomberg; J. Am.Chem. Soc.,.v0l. 42, .2067- 72 (1920). pp

1. THE PROCESS FOR THE PRODUCTION OF ORGANIC CARBONATES WHICH COMPRISESHEATING AT TEMPERATURES OF ABOUT 50* TO ABOUT 150* C. A SUBSTANTIALLYANHYDROUS MIXTURE OF CARBONATE OF SODIUM AND A COMPOUND SELECTED FROMTHE GROUP CONSISTING OF